Diene reaction products and process



reamed May 15, i945 DIENE REACTION PRODUCTS AND PROCESS Alexander A. Miller and Theodore F.

Bradley,

Stamford, Comp, assignors to American Cyanamid Company, New York, N. Y a corporation of Maine No Drawing. Application March 24, 1943,

- Serial No. 480,332

3 Claims.

This invention relates to a new series of synthetically prepared monomeric compounds, especially those obtained by reacting a compound containing one or more conjugated double bonds with an acrylic compound. More particularlyit embraces such compounds as alloiicimene-acrylonitrile addition products, myrcenevacrylonitrile addition products and similar adducts of diene-acrylic compounds and the processes for preparing such compounds.

It is an object of this invention to prepare these diene reaction products from relatively inexpensive and readily available raw materials.

It is a further object to prepare such products to serve as valuable intermediates suitable for use in the preparation of coating compositions,

metallic driers, plasticizers, and the like.

Still another object is to provide a process for the reaction 'of dienes such as alloocimene, myrcene and the like with vinyl compounds such as acrylonitrile. 7.

These and other objects are attained by reacting the particular diene compounds with acrylonitrile by heating equimolecular mixtures thereof under such conditions as those described in the accompanying examples forming a part of this invention.

The resultant compounds prepared as described below serve as intermediates for the production of a number of useful industrial compounds. The monomeric products of this invention as well as some of the polymeric compounds obtained therefrom have a wide field of application such, for example, as. modifiers for plastics, plasticizers for natural and synthetic rubber, adhesives and the like. When incorporated in such solvents as, for example, xylene, toluene, ketones, ethyl dichloride and the like, useful and valuable coating compositions are obtained.

The nitriles, amines, alcohols. acids and esters of the above. diene-acrylonitrile adducts also have a wide variety of commercial application.

For example, the nitriles and amines are useful insecticides and insect repellents. In particular, such derivatives as 5,5-dimethyl2-(a-methyl propenyl) 3 cyclohexene 1 carbonitrile has been found to be an especially efi'ective mosquito repellent. The amines also find use as surface active agents. The metallic salts of the acids are useful driers for coating compositions. The

esters are valuable plasticizers for gums, resins, natural and synthetic rubber and the like.

Thus it may be seen that these' diene adducts serve as very useful chemical intermediates and find application for various and sundry industrial purposes, particularly when prepared in accordance with the following detailed descriptive examples which illustrate specific embodiinents of the invention.

which is the polymer.

In the following examples, the proportions are given in parts by weight, the examples themselves being illustrative and not limltative of the invention.

EXAMPLE 1 REACTION MONOMER or ALLo'ticIMENs AND ACRYLONITRILE Alloiicimene 1105 g. (ca. 8 mols) Acrylonitrile 424 g. (ca. 8 mols) Hydroquinone 1.5 g. (ca. .1%)

The reaction is probably indicated as follows: CH3 /CH3 0E3 -/CH3I l c\ on 311, on +CHr=GH-CN CH oH-cN ll Acrylonitrlle R I FCH; fik-CH: E an OH on, H; I Alloficimcuc Adduct This mixture in the form of a solution is heated on an oil bath to C. at which temperature it refluxes. After refluxing for 60 hours, the temperature will be found to have risen to C. This indicates that most of the low boiling component, acrylonitrile, has been removed either by reaction with the alloiicimene or else by volatilization from the reaction mixture. The decrease in weight of 97 g. is accounted for by the distillation of acrylonitrile. The desired product, namely the allotScimene-acrylonitrile adduct, is obtained in a yield of 58.5%; 9% of The desired product is readily separated from the solution by fractional distillation at 1l5-120 C. under a pressure of 1 mm. of mercury.

The probable structural formula of the alloocimene-acrylonitrile adduct is:

CH: CH3

EXAMPLES 2 TO The myrcene-acrylonitrile reaction, however, gives. a much higher proportion 01 undesirable polymer. Thus in the above run 40% of the polymeric and 46% of the monomeric addition prod 5 not was obtained, while 13% of the myrceneg fi f ggg zz g ggg gfis z 222 1 3333 acrylonitrilesolution remained unreacted. The

. f m d t an utocl ve at fraction boiling at 100 C. to 123 C./l. mm. prespre em y came on m a a sure yields the desired product, a myrcene- 'MONOMERIC REACTION PRODUCT or ALLoocnasns em) ACRYLONITRILE UNDER SUPER-ATMOSPHERIC Paassmm Conm'rrous higher temperatures than those given in .acrylonitrile adduct, the major portion of which ample 1 and at super-atmospheric pressure. In distins over rapidly at 119L120.) (1/1 mm pres order to minimize oxidation and polymerization, sure v 0.1% hydroquinone is added. "The following A c 7 table gives a series of runs made at different is:The probable formula of this rea tion product temperatures and extending over difierent time intervals in order to obtain optimum conditions 5 for a maximum yield of product with a minimum 0 a CH, of polymer formation. In each of the examples H given below, equimolar reacting portions of alloocimene and acrylonitrile are heated with I a I .1 to 1% of hydroquinone in an autoclave. Frac- 1 tionation of the resultant product at 1 mm. merg, cury pressure, eliminating the first fraction ,boilmg below 100 C. as consisting principally of unreacted material, gives the-following results 9 in each example: Ct on Table 1 AUTOCLAVE REACTION OF ALLO6CIMENE WITH ACBYLO' NITRILE PRODUCT Example Temp., Time, B..P.et nu" Percent Percent ,Percent N0. C- hrs.

1 mm. yield polymer unrescted I Constant va r temperature. 1 Product dar yellow in color, indicating temperature of 175 C. was too high. I

summarizing the results obtained from Table Name: 4-6v-l h nyD-3- y 10heXene-1-carbo- 1, it is seen that heating the reactants at 150 mtrlle .C. for 12 hours as in Example 3 results in a preecu ar e t=189 ferred yield of the alloocimene acrylonitrile re- Boiling range=115-120 C./1 mm.

action product. =1.4895

du =0.9191 LE 6 EXAMPLE '1 Mouomuuc Rmcnon Pnonu'c'r or Mvncmu: AND flymoegmngn 0;- P D CT r En 1 ACRYmmm A sample of the alloocimene-acrylonitrile addi- Myrcene 2'72 g. (2 mols) tion product of Example 1 is readily hydrogen- Acrylonitrile 106 g. (2 mols) gated under super-atmospheric pressure with the Hydroquinone .3 g. 01%) aid of Raney nickel as a catalyst. The product A possessing a. strongly ammoniacal odor isreadlly The reaction is robably indmatedas follow s. separated by filtration from the ca 1 p to yield 3 a colorless liq d which upon standing exposed to en t: the air becomes reddish-brown in color. The 111- I n Q 5 trate is'iractionally distilled and the portions i a 4 boiling at 98 to 100 on mm, pressure comprise H E g Q g 00% oi. the total nitrate and make up the desired H, W o primary amine having the probable structural H i formula: 30 CH: CH:

' HI caca ea M V fig, i l

m it n on N13,

- C; CEa 5 rv r- I v seem This mixture is refluxed at first at a temneraa ture of 90 0. Alter refluxing for a period or tour a V v hours it is found that the temperature rises grad- Ha ually to 120 C.,- while the rate or refluxing de- Name: 3,3-dimethy1-8-(sec. butyli-i-cyelohexcreases with the increasing viscosity of the soluanemethylamine V tion. The resultant product is then jractionally Molecular weizht= 19l distilledunder a pressure of 1 mm. of mercury, Boilina rame=98-100 C./1 mm.

.the'unreacted myrcene and acrylonitrile being n "=1.4 89'1 stripped 0!! at vapor temperatureeup to C. d ==0,8848

asvaosv The undesired non-volatile residue comprising the remaining 20% is a secondary amine forming no part of the subject matter of the present application.

EXAMPLE 8 HYDROGENATION or 'rrm Pnonuc'r or EXAMPLE 6 H: I H:

Name: 4-isohexyl-l-cyclohexanemethylamine Molecular weight=197 Boiling range=l-120- C./1 mm. n =l.-1942 Neutral equivalent=190 (theory=197) A number of other monomeric materials which may be subsequently polymerized, or even used as the monomers, may likewise be obtained by reacting alloocimene, beta-myrcene, etc., with such products as dichloroacrylonitrile, dibromoacrylonitrile, methyl methacrylate, and the like. Such compounds as the above may be used to form copolymers with products such as butadiene, isoprene, pentadiene, dimethyl butadiene, chlorobutadienes, and the like. ermore, the com- Pounds of this invention either in monomeric or in polymeric form may be dissolved in any one of a number of suitable solvents for use in coating compositions, such solvents including toluene,

xylene, the ketones, ethyl dichloride, etc. Such coating compositions may have added thereto natural or synthetic drying oils as well as such resinous materials as any one of a number of phenol-formaldehyde condensation resins, more particularly such oil-soluble substituted phenolformaldehyde condensation products as p-tert.- amyl-phenol formaldehyde condensates. In addition various other resins such as the aminotriazine-formaldehyde condensation products, polyalcohol-polycarboxylic acid resins either modified with a fatty oil acid, ester gum, coumarone-indene resin, or in unmodified form may likewise be used to form coating compositiohs.

A compatible dye or various pigments may be incorporated in these coating compositions, examples being titanium dioxide, zinc oxide, iron oxide, malachite green, toluidine red, ochre, carbon black, etc. If desirable, fillers, extenders and the like may also be included such as wood dour, clay, glass wool, granite dust, sand, etc.

The above examples illustrate clearly that the use of more intensive reaction means such as may be effected with the aid of autoclaves, high-.pres- The products are useful ingredients for paper coating, textile coating or for coating other fibrous materials such as leather, as well as for impregnating and facilitating the penetration of various resinous materials into and between the fibers of similar fibrous materials. The heavy metal salts of acrylic acid-allodcimene addition products can be readily prepared by precipitation of such salts from an aqueous solution of a neutral potassium salt of the adduct product by such ions as Pb++, Mn+-+, Co++, Cu++, etc. The lead, manganous, and cobalt salts have properties similar to .the corresponding naphthenates and hence may be incorporated in driers for coating compositions.

The compounds of this invention may be used as plasticizers for adhesives, particularly for such tacky materials as natural and synthetic rubber in adhesive mixtures. 1

Many modifications and variations of the process and compounds described herein above may be made without departing from the spirit and scope of the invention as defined in the appended claims.

We claim:

1. A compound having the following probable formula:

CHO

F CH: (lg m-cN being the reaction product of equimolecular portions of alloocimene and acrylonitrile and characterized by the following properties: a molecular weight of 189, a boiling range of HES-120 C. at 1 mm. pressure of mercury, refractive index n =L4948 and density dzt= =0.9l07.

2. The method of preparing an alloocimeneacrylonitrile adduct which comprises reacting allodcimene and acrylonitrile at a temperature of C. initially, increasing the temperature to approximately 135-l50 C. over a period of 12 to 60 hours and separating out the desired adduct by fractional distillation at -l20 C. and under a pressure of 1 mm. of mercury.

3. The method of reparing an alloocimeneacrylonitrile adduct which comprises refluxing equi-molecular portions of allodcimene andv acrylonitrile on an oil bath initially at a temperature of 90 C. increasing the temperatureto approximately -150 C, over a period of 12 to 60 hours and separating out the desired adduct in monomeric form by fractional distillation at 115-120 C. and under a pressure of 1 mm. of 

